Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0095—Mixtures of at least two compounding ingredients belonging to different one-dot groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
  • C08L75/06—Polyurethanes from polyesters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
  • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
  • C08J2375/04—Polyurethanes
  • C08J2375/06—Polyurethanes from polyesters
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/02—Organic and inorganic agents containing, except water
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
  • Y10S516/06—Protein or carboxylic compound containing
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
  • Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
  • Y10S516/906—The agent contains organic compound containing silicon

Definitions

• This composition is useful as a surfactant in the preparation of flexible polyester based polyurethane foams where it minimizes problems of splitting and shrinkage of the foams, promotes uniformity of cell size, promotes compatibility of the reactants and catalyst, and allows wider processing and formulation latitude.
• polyester based polyurethane foams are described numerous places in the literature. Reference may be had, for example, to US. Patent Re. 24,514, the disclosure of which is incorporated herein by reference, for a disclosure of specific examples of the basic components used in preparing such a foam and for a processing technique for preparing such foams.
• this invention relates to a composition which consists essentially of (1) 75 to 95 percent by Weight of a trimethylsilyl endblocked siloxane-polyoxyethylene copolymer of the general formula sh K Q h K m 0 Q NM n has a value of from 1 to 8, x has an average value of from 2 to 12, y has an average value of from 8 to 60, and A is a capping group, and
• This invention further relates to an improvement in a process of preparing a flexible polyester based polyurethane foam wherein a surfactant is employed to control cell size and/ or stabilize the foam, the improvement which comprises employing as the surfactant the composition as defined above.
• siloxane-polyoxyethylene copolymers employed in the composition and process of this invention can be pre- 3,655,581 Patented Apr. 11, 1972 pared by the well known process of adding a terminally unsaturated polyoxyethylene glycol to the appropriate Si-H containing siloxane in the presence of a suitable catalyst such as chloroplatinic acid.
• a suitable catalyst such as chloroplatinic acid.
• the operable polyoxyethylene-siloxane copolymers are those which are trimethylsilyl endblocked and contain from 1 to 8 (methyl)polyoxyethylene siloxane units in the chain.
• n can be 1, 2, 3, 4, 5, 6, 7, or 8, generally speaking a mixture of these species will be used since it is much more economical and there is little difference if any in the performance obtained.
• copolymers contain no dimethylsiloxane units in the chain.
• the presence of such units, particularly in significant amounts has a detrimental effect on a polyester based polyurethane foam prepared from it.
• the polyoxyethylene portion of the copolymer is attached to the silicon atom via an alkylene bridge, usually a polymethylene bridge, as can readily be seen from. the above formula.
• This alkylene bridge can contain, on an average, from 2 to 12 carbon atoms, that is to say, x has an average value of from 2 to 12.
• y has an average value of from 8 to 60.
• the polyoxyethylene unit is terminated or capped by the A group.
• the polyoxyethylene unit can be capped by a hydroxyl group (A is a hydrogen atom), by an ether group -(A is a monovalent hydrocarbon radical such as a methyl, butyl, vinyl or phenyl radical), by a carboxyl radical, by the salt or ester of a carboxyl radical, or a carbonate ester group.
• A is a hydrogen atom
• the second component of the composition of this invention is a fatty acid having from 10 to 40 carbon atoms.
• the fatty acids useful herein can be either saturated or unsaturated, monobasic or poly-basic, acids.
• the term fatty acid as employed herein is also intended to include the dimerized or trimerized fatty acids. While it is possible to use the individual species, it is preferred to employ mixtures of the fatty acids since they occur naturally in such mixtures and are frequently marketed as such.
• Specific examples of fatty acids that can be employed herein include lauric, oleic, stearic and n-octatrtiacontanoic acid.
• Specific examples of mixtures of fatty acids that can be employed herein include the tall oil fatty acids and soybean fatty acids.
• An example of a suitable commeroial dimer acid is a C aliphatic dibasic acid prepared by the dimerization of a C unsaturated fatty acid and is sold under the trademark Empol 1024.
• the amount of the above composition employed in preparing a polyester based polyurethane foam will vary depending upon the exact characteristics desired in the final product, the specific process and fonmulation used, and individual preferences. Generally speaking, however, the
• composition employed will be within the range of 0.1 to 2.0 (preferably 0.5 to 1.0) percent based on the total weight of the polyurethane foam composition.
• EXAMPLE 1 A mixture 'was prepared which consisted essentially of 3 parts of water, 1 part of N-ethyl morpholine, 0.2 part N,N-dimethyl hexadecyl amine and 1 part of a composition which consisted essentially of 90 percent of a siloxane-polyoxyethylene copoly mer consisting essentially of about 63 mol percent (CH );SiO[(CH )SiO]Si(CH ((IJZHAO)-I2H and about 37 mol percent of a)t l( a) ]2 s)a 0 (J72H4O)-12H and about percent of a C dimer acid (Empol 1024).
• a siloxane-polyoxyethylene copoly mer consisting essentially of about 63 mol percent (CH );SiO[(CH )SiO]Si(CH ((IJZHAO)-I2H and about 37 mol percent of a)
• glycoladipate polyester polyurethane resin in a one quart paper cup.
• the resin and the premix were mixed for about 30 seconds at 1200 r.p.m. and then a 3 percent excess (103 Index) of toluene diisocyanate was added to the paper cup and mixed again for 5 seconds at 1000 r.p.m.
• the resulting mix was then poured into a three quart paper bucket and allowed to foam unrestricted. This resulted in a very good polyurethane foam having uniform cell size.
• Example 2 The procedure of Example 1 was repeated except that the initial composition contaned 4 parts of Water and 2 parts of N-ethyl morpholine. Essentially identical results were obtained.
• EXAMPLE 3 Two polyester based polyurethane foams were prepared by adding 10.8 g. of a premix to 150 g. of a commercial glycol-adipate polyester resin (Fomrez 50) and mixing for 30 seconds at 1200 r.p.m. and then adding 58.5 cc. of toluene diisocyanate and mixing 5 seconds at 1000 r.p.m. The resulting mix was poured into a three quart paper bucket and allowed to foam unrestricted. Upon completion of the rise the foam was allowed to cure.
• the premixes consisted of 4 parts of water, 2 parts N-ethyl morpholine, 1 part surfactant and 0.2 part N,N- dimethyl hexadecyl amine.
• the surfactant was a composition consisting essentially of (1) about 90 percent of siloxane-polyoxyethylene copolymer consisting essentially of about 62 mol percent I I (C2H4O)-I2H and about 38 mol percent aMS K a) h K Ha):
• the surfactant was a composition consisting essentially of (1) about percent of the siloxane-polyoxyethylene copolymer mixture wnmsiotwnn hsiwntn I (orang tulotwn and (2) about 10 percent of C dimer acid Empol 1024).
• the above prepared foams had the following characteristics.
• t 100 parts of a commercial 'glycol-adipate polyester resin (Fomrez 50), 3 parts water, 1 part N-ethyl morpholine, 1 part of a surfactant composition consisting essentially of (1) 90 percent of I a)a t) lr-z K flsh (CzH4O)-izH and (2) 10 percent oleic acid, 0.2 part N,N-di
• Foam I had a rise time of 72.2 seconds whereas foam II had a rise time of 72 seconds. Both were good foams having uniform cell size and with foam I being somewhat finer celled than foam II.
• EXAMPLE 7 A mixture having a ratio of 100 parts of a commercial glycol-adipate polyester polyurethane resin and 10 parts of trichloromonofluoromethane was prepared. To 140 parts of the foregoing mixture there was added 6.62 parts of a premix having a trio of 3 parts water, 1 part N-ethylmorpholine, 1 part of a surfactant composition and 0.2 part N,N-dimethyl hexadecyl amine and then the two mixed for 30 seconds at 1200 r.p.m. Then 39.6 ml. of toluene diisocyanate (3 percent excess) was added and mixed for 5 seconds at 1000 r.p.m.
• the resulting mix was poured into a three quart paper bucket and allowed to foam unrestricted, and then cured.
• Two different surfactant compositions and two toluene diisocyanates (80/20 and 65/35 ratios of the 2,4 and 2,6 isomers) were used.
• Surfactant I was a composition consisting essentially of 1) 90 percent of and (2) percent of C dimer acid.
• Surfactant II was identical to surfactant I except that it contained 80 percent (1) and percent (2).
• the foams in all cases were good with those from the 65 35 toluene diisocyanate being finer celled foams. The rise times of the various foams is set forth below.
• a polyester based polyurethane foam was prepared by mixing 100 parts of a commercial glycol-adipate polyester resin (Fomrez 50), 4 parts of water, 2 parts of N-ethyl morpholine, 0.2 part N,N-dimethyl cetyl amine, 0.1 part dimer acid (Empol 1024) and 0.9 part of a composition consisting essentially of EXAMPLE 9
• a commercial glycol-adipate polyester resin Fomrez 50
• 4 parts of water 2 parts of N-ethyl morpholine
• N,N-dimethyl cetyl amine 0.1 part dimer acid (Empol 1024)
• dimer acid dimer acid
• polyester based polyurethane foams are obtained which have uniform cell size and in which problems of splitting and shrinkage are minimal.
• composition which consists essentially of (l) 87 percent of a)a a) ]2 Ha)a 6 2H40heC Hn and (2) 13 percent stearic acid.
• composition which consists essentially of (1) 83 percent of 3)3 l( a) l1s :)a
• composition which consists essentially of (1) 90 percent of 0 6 l! 2 4O)a s 5 and (2) 20 percent tall oil fatty acids.
• a composition which consists essentially of (1) 75 to percent by 'weight of a trimethylsilyl endblocked siloxane-polyoxyethylene copolymer of the general formula (CH SiO[(CHa)Si0]nSi(OH wherein n has a value of from 1 to 8, x has an average value of from 2 to 12, has an average value of from 8 to 60, and A is a capping group selected from the group consisting of the hydrogen atom, monovalent hydrocarbon radicals, carboxyl radicals, salts of carboxyl radicals, esters of carboxyl radicals and carbonate esters, and
• composition as defined in claim 1 wherein 50 to 75 mol percent of (1) is the species wherein n is 1 and 25 to 50 mol percent of (1) is the species wherein n is 2, x is 3, y has an average value of about 12, A is a hydrogen atom, and (2) is a dimer acid.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Polyurethanes Or Polyureas (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=25065580

Family Applications (1)

Country Status (11)

Cited By (2)

• 1968
  • 1968-09-25 US US762613A patent/US3655581A/en not_active Expired - Lifetime
• 1969
  • 1969-05-02 JP JP44033652A patent/JPS5147759B1/ja active Pending
  • 1969-05-14 BR BR208822/69A patent/BR6908822D0/pt unknown
  • 1969-05-20 SE SE07138/69A patent/SE350762B/xx unknown
  • 1969-08-22 DE DE19691942869 patent/DE1942869A1/de active Pending
  • 1969-08-26 GB GB42445/69A patent/GB1243582A/en not_active Expired
  • 1969-08-27 AT AT08192/69A patent/AT294431B/de not_active IP Right Cessation
  • 1969-09-23 FR FR6932367A patent/FR2018829A1/fr not_active Withdrawn
  • 1969-09-24 BE BE739311D patent/BE739311A/xx not_active IP Right Cessation
  • 1969-09-25 CH CH1447969A patent/CH528297A/de not_active IP Right Cessation
  • 1969-09-25 NL NL6914540A patent/NL6914540A/xx unknown

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